The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional....The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional. The complex is connected through two different types of inter-molecular hydrogen bonds. After photo-excitation, both hydrogen bonds get strengthened, which can facilitate the ESDPT reaction. The scanned potential energy curve along the proton transfer coordinate indicates that the ESDPT reaction proceeds in a stepwise pattern.展开更多
The effect of iridium loading on the properties and catalytic isomerization of n-heptane over Ir-HZSM-5 is studied. Ir-HZSM-5 was prepared by impregnation method and subjected to isomerization process in the presence ...The effect of iridium loading on the properties and catalytic isomerization of n-heptane over Ir-HZSM-5 is studied. Ir-HZSM-5 was prepared by impregnation method and subjected to isomerization process in the presence of flowing hydrogen gas. XRD and BET studies show that the presence of iridium stabilizes the crystalline structure of HZSM-5, leading to more ordered framework structure and larger surface area. TGA and FTIR results substantiate that iridium species interacts with OH group on the surface of HZSM-5. Pyridine FT-IR study verifies the interaction between iridium and surface OH group slightly increased the Bro¨nsted and Lewis acid sites without changing the lattice structure of HZSM-5. The presence of iridium and the increase of strong Lewis acid sites on HZSM-5 were found to bring an increase about 4.1%, 33.2% and 11.8% in conversion, selectivity and yield of n-heptane isomerization, respectively.展开更多
Ni/PtHY with different Ni loadings was prepared by impregnating HY with hexachloroplatinic acid solution and Ni2＋/N,N-dimethylformamide solution. An increase in the Ni loading decreased the crystallinity, specific su...Ni/PtHY with different Ni loadings was prepared by impregnating HY with hexachloroplatinic acid solution and Ni2＋/N,N-dimethylformamide solution. An increase in the Ni loading decreased the crystallinity, specific surface area and meso-micropores of the catalysts. Ni interacted with hydroxyl groups to produce IR absorption bands at 3740-3500 cm-1, Increasing Ni loadings resulted in a decrease in the intensities of the broad bands at 3730-3500 cm-1 and the sharp band at 3740 cm-1 with simultaneous development of new absorbance band at 3700 cm-1 that was attributed to （-OH）Ni. The acidity of the samples did not significantly change with Ni loadings up to 1.0 wt%, which indicated that Ni mostly interacts with non-acidic silanol groups （terminal- and structural-defect OH groups）. The presence of Ni decreased the activity of PtHY toward the isomerization of n-pentane because of a decrease in the number of active protonic-acid sites that formed from molecular hydrogen. IR and ESR studies confirmed that Pt facilitated the formation of protonic-acid sites from molecular hydrogen, whereas Ni, even when combined with Pt, didn＇t exhibit such ability. The absence of protonic-acid sites from molecular hydrogen significantly decreased the yield of iso-pentane and markedly increased the cracking products.展开更多
Polybenzimidazole containing ether bond（OPBI） was reinforced with silicon carbide whisker（m Si C） modified by 3-aminopropyltriethoxysilane（KH550）, and then doped with phosphoric acid（PA） to obtain OPBI/m Si C/...Polybenzimidazole containing ether bond（OPBI） was reinforced with silicon carbide whisker（m Si C） modified by 3-aminopropyltriethoxysilane（KH550）, and then doped with phosphoric acid（PA） to obtain OPBI/m Si C/PA membranes. These OPBI/m Si C/PA membranes have excellent mechanical strength and oxidative stability and can be used for high temperature proton exchange membrane（HT-PEM）. The tensile strength of OPBI/m Si C/PA membranes ranges from 27.3 to 36.8 MPa, and it increases at first and then decreases with the increase of m Si C content. The high m Si C content and PA doping level contribute to improving the proton conductivity of membranes. The proton conductivity of PBI/m Si C-10/PA membrane is 27.1 m S cm-1 at 170℃ without humidity, with an increase of 55.7% compared with that of OPBI/PA membrane. These excellent properties make OPBI/m Si C/PA membranes promising membrane materials for HT-PEM applications.展开更多
文摘The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional. The complex is connected through two different types of inter-molecular hydrogen bonds. After photo-excitation, both hydrogen bonds get strengthened, which can facilitate the ESDPT reaction. The scanned potential energy curve along the proton transfer coordinate indicates that the ESDPT reaction proceeds in a stepwise pattern.
基金supported by the Ministry of Science,Technology and Innovation,Malaysia through E-Science Fund Research Project(No.03-01-06-SF0564 and 03-01-06-SF0289)the Hitachi Scholarship Foundation for the Gas Chromatograph Instrument Grant
文摘The effect of iridium loading on the properties and catalytic isomerization of n-heptane over Ir-HZSM-5 is studied. Ir-HZSM-5 was prepared by impregnation method and subjected to isomerization process in the presence of flowing hydrogen gas. XRD and BET studies show that the presence of iridium stabilizes the crystalline structure of HZSM-5, leading to more ordered framework structure and larger surface area. TGA and FTIR results substantiate that iridium species interacts with OH group on the surface of HZSM-5. Pyridine FT-IR study verifies the interaction between iridium and surface OH group slightly increased the Bro¨nsted and Lewis acid sites without changing the lattice structure of HZSM-5. The presence of iridium and the increase of strong Lewis acid sites on HZSM-5 were found to bring an increase about 4.1%, 33.2% and 11.8% in conversion, selectivity and yield of n-heptane isomerization, respectively.
基金supported by the Ministry of Higher Education, Malaysia through Fundamental Research (Grant Scheme No. 78670)the UTM Short Term Research (Grant No. 77330)
文摘Ni/PtHY with different Ni loadings was prepared by impregnating HY with hexachloroplatinic acid solution and Ni2＋/N,N-dimethylformamide solution. An increase in the Ni loading decreased the crystallinity, specific surface area and meso-micropores of the catalysts. Ni interacted with hydroxyl groups to produce IR absorption bands at 3740-3500 cm-1, Increasing Ni loadings resulted in a decrease in the intensities of the broad bands at 3730-3500 cm-1 and the sharp band at 3740 cm-1 with simultaneous development of new absorbance band at 3700 cm-1 that was attributed to （-OH）Ni. The acidity of the samples did not significantly change with Ni loadings up to 1.0 wt%, which indicated that Ni mostly interacts with non-acidic silanol groups （terminal- and structural-defect OH groups）. The presence of Ni decreased the activity of PtHY toward the isomerization of n-pentane because of a decrease in the number of active protonic-acid sites that formed from molecular hydrogen. IR and ESR studies confirmed that Pt facilitated the formation of protonic-acid sites from molecular hydrogen, whereas Ni, even when combined with Pt, didn＇t exhibit such ability. The absence of protonic-acid sites from molecular hydrogen significantly decreased the yield of iso-pentane and markedly increased the cracking products.
基金financially sponsored by the Kunlun Scholar Award Program of Qinghai Provincethe Fundamental Research Funds for the Central Universities (WD1315012)
文摘Polybenzimidazole containing ether bond（OPBI） was reinforced with silicon carbide whisker（m Si C） modified by 3-aminopropyltriethoxysilane（KH550）, and then doped with phosphoric acid（PA） to obtain OPBI/m Si C/PA membranes. These OPBI/m Si C/PA membranes have excellent mechanical strength and oxidative stability and can be used for high temperature proton exchange membrane（HT-PEM）. The tensile strength of OPBI/m Si C/PA membranes ranges from 27.3 to 36.8 MPa, and it increases at first and then decreases with the increase of m Si C content. The high m Si C content and PA doping level contribute to improving the proton conductivity of membranes. The proton conductivity of PBI/m Si C-10/PA membrane is 27.1 m S cm-1 at 170℃ without humidity, with an increase of 55.7% compared with that of OPBI/PA membrane. These excellent properties make OPBI/m Si C/PA membranes promising membrane materials for HT-PEM applications.
